Catalyst component for olefin polymerization, catalyst, and use thereof

Patent metadata

Field	Value
Publication number	US-9751960-B2
Application number	US-201414892533-A
Country	US
Kind code	B2
Filing date	May 21, 2014
Priority date	May 21, 2013
Publication date	Sep 5, 2017
Grant date	Sep 5, 2017

Abstract

The present disclosure provides a solid catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen, and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds as shown in Formula (I). The catalyst according to the present disclosure has significantly improved polymerization activity, hydrogen response, and stereoselectivity. According to the present disclosure, when the catalyst system containing a diol diester compound as shown in Formula (I) of the present disclosure is used in olefin polymerization, the catalyst shows good comprehensive performance, including high catalytic activity. In particular, in the presence of highly concentrated hydrogen, the catalyst has an improved hydrogen response and/or isotacticity of the polymers obtained can be significantly improved. The catalyst of the present disclosure is beneficial for obtaining polymers with a high melt index and high isotacticity, and for development of polymers of different grades.

First claim

The invention claimed is:

1. A catalyst component for olefin polymerization, comprising magnesium, titanium, a halogen, and an electron donor, wherein the electron donor is at least one selected from the group consisting of diol diester compounds, wherein the diol diester compounds are one or more selected from the group consisting of 2,4-hexanediol-bis(4-ethyl benzoate),
2,4-hexanediol-bis(4-n-propyl benzoate),
2,4-hexanediol-bis(4-n-butyl benzoate),
2,4-hexanediol-bis(4-iso-butyl benzoate),
2,4-hexanediol-bis(4-tert-butyl benzoate),
2,4-hexanediol-bis(4-hexyl benzoate),
3-methyl-2,4-hexanediol-bis(4-ethyl benzoate),
3-methyl-2,4-hexanediol-bis(4-n-propyl benzoate),
3-methyl-2,4-hexanediol-bis(4-n-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-iso-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-tert-butyl benzoate),
3-methyl-2,4-hexanediol-bis(4-hexyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-ethyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-n-propyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-n-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-iso-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-tert-butyl benzoate),
3-ethyl-2,4-hexanediol-bis(4-hexyl benzoate),
3,5-heptanediol-bis(4-n-propyl benzoate),
3,5-heptanediol-bis(4-iso-propyl benzoate),
3,5-heptanediol-bis(4-iso-butyl benzoate),
3,5-heptanediol-bis(4-tert-butyl benzoate),
3,5-heptanediol-bis(4-pentyl benzoate),
3,5-heptanediol-bis(4-hexyl benzoate),
3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-methyl-3,5-heptanediol-bis(4-ethyl benzoate),
4-methyl-3,5-heptanediol-bis(4-n-propyl benzoate),
4-methyl-3,5-heptanediol-bis(4-iso-propyl benzoate),
4-methyl-3,5-heptanediol-bis(4-n-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-iso-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-3,5-heptanediol-bis(4-pentyl benzoate),
4-methyl-3,5-heptanediol-bis(4-hexyl benzoate),
4-methyl-3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-ethyl-3,5-heptanediol-bis(4-ethyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-n-propyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-iso-propyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-n-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-iso-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-pentyl benzoate),
4-ethyl-3,5-heptanediol-bis(4-hexyl benzoate),
4-ethyl-3,5-heptanediol-cinnamic acid-4-ethyl benzoate,
4-n-propyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-n-butyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4,4-dimethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-4-ethyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
4-methyl-4-n-propyl-3,5-heptanediol-bis(4-tert-butyl benzoate),
3-methyl-2,4-heptanediol-bis(4-n-propyl benzoate),
3-methyl-2,4-heptanediol-bis(4-iso-propyl benzoate),
4-methyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-ethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-n-propyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-n-butyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,4-dimethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,4-diethyl-3,5-octanediol-bis(4-n-propyl benzoate),
4,4-di-n-propyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4-methyl-4-ethyl-3,5-octanediol-bis(4-tert-butyl benzoate),
4,6-nonanediol-bis(4-ethyl benzoate),
4,6-nonanediol-bis(4-n-propyl benzoate),
4,6-nonanediol-bis(4-n-butyl benzoate),
4,6-nonanediol-bis(4-iso-butyl benzoate),
4,6-nonanediol-bis(4-tert-butyl benzoate),
4,6-nonanediol-bis(4-hexyl benzoate),
4,6-nonanediol-cinnamic acid-4-ethyl benzoate,
5-methyl-4,6-nonanediol-bis(4-ethyl benzoate),
5-methyl-4,6-nonanediol-bis(4-n-propyl benzoate),
5-methyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-iso-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-methyl-4,6-nonanediol-bis(4-hexyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-ethyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-n-propyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-iso-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-ethyl-4,6-nonanediol-bis(4-hexyl benzoate),
5-n-propyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5-n-butyl-4,6-nonanediol-bis(4-n-butyl benzoate),
5,5-dimethyl-4,6-nonanediol-bis(4-tert-butyl benzoate),
5,5-diethyl-4,6-nonanediol-bis(4-hexyl benzoate),
5,5-di-n-propyl-4,6-nonanediol-bis(4-pentyl benzoate), and
5,5-dibutyl-4,6-nonanediol-bis(4-tert-butyl benzoate).

2. The catalyst component according to claim 1 , wherein the catalyst component is prepared by reacting magnesium compounds, titanium compounds, and the diol diester compounds.

3. The catalyst component according to claim 2 , wherein the magnesium compounds are selected from the group consisting of magnesium dihalides, alkoxy magnesium compounds, alkyl magnesium compounds, hydrates or alcoholates of magnesium dihalides, and derivatives of magnesium dihalides with halogen atoms thereof being substituted by alkoxy groups or halogenated alkoxy groups; and
wherein the titanium compounds have a general formula of TiX m (OR 1 ) 4-m , with R 1 being a C 1 to C 20 hydrocarbyl group, X a halogen, and 1≦m≦4.

4. The catalyst component according to claim 2 , wherein based on one mole of the magnesium compounds, the dosage of the titanium compounds is in the range from 0.5 mole to 150 mole, and that of the diol diester compounds is in the range from 0.01 mole to 5 mole.

5. A catalyst for olefin polymerization, comprising the following components: component a): the catalyst component according to claim 1 ; and
component b): alkylaluminum compounds.

6. The catalyst according to claim 5 , further comprising component c): an external electron donor, which is selected from the group consisting of organosilicon compounds, ethers, and esters.

7. The catalyst according to claim 6 , wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum is in the range from 1:5 to 1:1,000, and/or the molar ratio of component c) to component a) is in the range from 0:1 to 500:1.

8. A prepolymerization catalyst for olefin polymerization, comprising the catalyst according to claim 5 , and a prepolymer generated by prepolymerization between said catalyst and olefins, with the prepolymerization multiples thereof being 0.1 g to 1,000 g of olefin polymers per g of the catalyst component.

9. A method for olefin polymerization, wherein an olefin is contacted under polymerization conditions with the catalyst component according to claim 1 .

10. The method according to claim 9 , wherein the olefins have a general formula of CH 2 ═CHR, with R being hydrogen or a C 1 to C 12 alkyl or aryl group.

11. The catalyst component according to claim 3 , wherein based on one mole of the magnesium compounds, the dosage of the titanium compounds is in the range from 0.5 mole to 150 mole, and that of the diol diester compounds is in the range from 0.01 mole to 5 mole.

12. The catalyst according to claim 6 , wherein the molar ratio of component a) to component b) based on the molar ratio of titanium to aluminum is in the range from 1:5 to 1:1,000, and/or the molar ratio of component c) to component a) is in the range from 0:1 to 500:1.

13. A method for olefin polymerization, wherein an olefin is contacted under polymerization conditions with the catalyst according to claim 5 .

14. The method according to claim 13 , wherein the olefins have a general formula of CH 2 ═CHR, with R being hydrogen or a C 1 to C 12 alkyl or aryl group.

15. A method for olefin polymerizat

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Li Changxiu
• Gao Mingzhi
• Liu Haitao
• Chen Jianhua
• Ma Jing
• Ma Jixing
• Cai Xiaoxia
• Wang Jun
• Zhang Xiaofan
• Hu Jianjun

Classifications

• C08F10/06 Primary

  Propene · CPC title

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title

• C08F110/06

  Propene · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• C08F2500/15

  Isotactic · CPC title